Azo compounds and material colored therewith



Patented Nov. 4, 1941 UNITED STATES"; ATENT .OFFlCE AZO COMPOUNDS ANlj MATERIAL COLORED THEREWITH James G. McNally and Joseph B. Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y,, a corporation of New I Jersey No Drawing. Application July 1, 1939, Serial No. 282,526

7 Claims. (Cl-- 260-205) This invention relates to the preparation of a new series of azo dyes. More particularly the invention relates to azo compound-s containing at least one sulfonamide group as a substituent on a nitrobenzene nucleus.

We have found that a valuable series of azo dyes suitable for the coloration of organic derivatives of cellulose, particularly cellulose acetate, can be prepared by coupling various aryl coupling components with the diazonium derivatives of the following general type of arylamines:

, wherein R1 and R2 have the above meanings.

The chemical structure of our azo dyes is represented by the following general formula:

prepare the dyes of the class above described and to color cellulose organic derivatives, particularly cellulose acetate in the form of threads, yarns, filaments, and fabric materials therewith.

The amino compounds used in our invention as the diazo components are prepared by halo- 1 -nitro-2 -aminobenzene sulfonamide, 5-m'tro-2- -a'minobenzenesulfonmethyl amide, 5-nitro-2- genating, nitrating, or sulfonating with chlorosulfonic acid the necessary aryl compounds and reacting with ammonia or various amines as desired. For example, thesulfonated nitro anilines of the type:

NO- NH:

' R( V OBN wherein R1 and R2 have the meanings already given, may be prepared by heating p-nitroaniline, p-nitro-o-haloaniline, p-nitro-o-alkylaniline and the like with chlorosulfonic acid and treating with an amine.

The monosulfonamide derivatives such as 5- aminobenzene sulfondimethyl amide, 5-nitro -2- amino-benzenesulfon ethylamide, 3,5-dinitro-2- amino-benzenesulfonmethylamide, and various other similar types of compounds may be prepared by the general method described by P. Fischer, Berichte der deutschen Chemischen Gesellschaft, volume 24, page 3790', (1891).

The following examples illustrate'the preparation of the azo compounds of our invention.

Example 1 (A) 6.9 grams of sodium nitrite are dissolved at 15 C. in 53 c. c. of sulfuric acid, the mixture warmed at 70 C. and then cooled to 10-15 C.

(B) 21.7grams of 5-nitro-2-aminobenzene sulfonamide are dissolved in 220 c. c. of hot acetic acid and rapidly cooled to 10-15 C.

The diazotization is carried out byadding solution (B) to solution (A) over a period of 30-45 minutes, meanwhile maintaining a temperature of 10-15 0., and stirring continuously. When the addition is complete, the mixture is further stirred at room temperature for one hour.

The coupling reaction is performed by dissolving 18.1 grams of di-p-hydroxyethylaniline in cold hydrochloric acid, adding ice, and then stirring into this solution the diazo mixture prepared above. :After standing for a short time,,the mixture is made neutral to Congo indicating paper with sodium acetate, and when coupling is complete, the dye is filtered, washed and dried. cellulose acetate is colored rubine shades from aqueous dispersions of the dye.

The dye compound has the formula:

CzHrOH CZHAOH OaNH:

Example 2 C7115 O H \C2H4OH S OzN Example 3 29.3 grams of 5-nitro-2-aminobenzene sulfonylanilide are diazotized and coupled with 21.6 grams of di-B-hydroxyethyl-m-chloroaniline following the procedure described in Example 1. The dye colors cellulose acetate red shades from aqueous dispersions of the dye.

The dye compound has the formula:

CZHlOH O N O N -N N /H 61 CQHAO H Example 4 (A) 7 grams of sodium nitrite are dissolved in 50 c. c. of sulphuric acid at 10-15 C., the solution heated to 70 C., and then cooled to 10-15 C.

(B) 29.6 grams of 2-amino-3-bromo-5-nitrobenzenesulfonamide are dissolved in 220 c. c. of hot acetic acid and rapidly cooled.

The diazotization is carried out by adding solution (B) to solution (A) over a period of 30-45 minutes, meanwhile maintaining a temperature of 10-15" 0., and stirring continuously. When the addition is complete, the mixture is further stirred at room temperature for one hour, and then 1 gram of urea is added.

The coupling reaction is performed by dissolving 18.1 grams of di-fl-hydroxyethylaniline in dilute hydrochloric acid, adding ice, and then stirring into this solution, the diazo mixture prepared above. After standing for a short time, the mixture is made neutral to Congo with sodium acetate, and when coupling is complete, the dye is filtered off, washed and dried. Cellulose acetate is colored rubine shades from aqueous dispersions of the dye.

The dye compound has the formula:

I CZHAOH CzHrOH amide-aminobenzene are diazotized and coupled with 31.1 grams of glycerylcresidine following the procedure described in Example 4. Cellulose acetate is colored violet shades from aqueous dispersions of the dye.

The dye compound has the formula:

CHa

SOzN

CH (1)0113 l1 N0 N=N N CH3 CH1 CH5 l SOzN CHOllCHzOH Example 6 24.7 grams of 2-amino-3-methoxy-5-nitrobenzene sulfonamide are diazotized as described in Example 4, and coupled with one equivalent of sodium butyl-sulfate ethyl-m-chloroaniline in water. When the coupling reaction is complete, the dye is salted out, washed and dried. Cellulose acetate is colored rubine shades from aqueous suspensions of the dye.

The 2.20 compound produced has the formula:

OCH:

CzHt N02 N=N N\ clmsomu 0mm 01 Example 7 NO: 0 CH3 /H N02 N=N- N\ H I CHz-CHOH-CHaOH CH5 S OzN In place of glyceryl cresidine there may be used, 3,6-dimethoxy-glyceryl aniline, ethyl glyceryl aniline, and 3-carbamide-fi-methoxy-di-fihydroxyethylaniline. In each case the dye compound colors cellulose acetate violate shades, except B-carbamide 6 methoxy-di p hydroxy ethylaniline which colors cellulose acetate a blue shade from an aqueous solution of the dye.

The diazo component may likewise be replaced by other 2-amino-3,5-dinitrobenzene sulfonamide compounds such as 2-amino-3,5-dinitrobenzene sulfonmethylamide, 2-amino-3-5- dinitrobenzene sulfonhydroxyethylamide, 2- amino-3,5-dinitrobenzene sulfondibutylamide, 2- amino-3,5-dinitrobenzene sulfon-B-sodium sulfoethylamide and other similar type of 2-amino 3,5 -dinitrobenzenesulfonomonoand dialkylamides, and coupled with the above mentioned coupling components to yield dye compounds which color cellulose acetate purple and blue shades.

Example 8 One mole of 2-amino-3,5-dinitrobenzene sulfonmethylamide is diazotized and added with stirring to a cold acetic acid solution of one mole of di-p-hydroxyethy1-m-toluidine. After standing for 15-30 minutes, the mineral acid is neuquinoline there may be substituted 'N-glyceryl tetrahydroquinoline which produces violet shades on cellulose acetate from aqueous suspensions of the dye.

tralized and the dye precipitated with water and E Z ice. Cellulose acetate is colored violet shades ramp 6 E152;ittifiilft ffiifbiifii $231118 forone mole of 2amino-3,5enema-mememula, ethylsulfonamide is diazotized and coupled with N02 10 one mole of 2-ethoxy-5-acety1aminoethyl glyc- CZHAOH eryl aniline following the procedure described in N02 N=N Example 9. Cellulose acetate is colored bluegreen shades from aqueous suspensions of the /H CH CzH4QH dye z SOQN The azo compound prepared as above has the CH3 formula: In place of di-p-hydroxyethyl-m-toluidine OGIH CzHs there may be substituted allyl-m-toluidme, cyclohexyl-m-teluidine, tetrahydrofurfuryl-m-to- N O N=N luidine, di-,3-methoXyethy1-m-toluidine, and dioniononcnzon hydroxy-propyl-m-toluidine.

Example 9 SOzN 000113 One mole of 2-amino-3,5-dinitro-sulfonethylozHoom a g q and hfi i In place of 2-ethoxy-5-acetylamino-ethyl glyc- 'i e 2 37 i erylaniline there may be substituted 3-formylam- 3 i fi 1 a an fi g inc-ethyl aniline, 3-lactyl-amino-di-B-hydroxyt i neu 3 ethyl aniline, 2-ethoxy-5-butyrylamino-ethyl fi- 3 an 0 glycerylaniline, 2-chloro-5-benzoy1amino-,8-hy- Ce 056%? a es Tom aque' droxyethylaniline, 2-methy1-5-furoylamino-ethy1 Ous Suspenslons 0 t e bz j h th f ul glyceryl aniline, 2-ethoxy-5-palmitylamino-ethyl The azo compound 0 amed as 6 011m glycerylaniline, 3-carbamino-ethyl glyceryl anil- CH2OHOHCH20H ine, 2-ethoxy-5-cyanoacety1amino-ethyl glyceryl- 1; aniline, 3-methylsulfonamino-p-hydroxyethylan- NO: CH: 32 iline, and similar kinds of compounds.

I The invention is further illustrated by refer- O ence to the following table. The compound listed H under the heading Amine is diazotized and S O coupled with an equivalent quantity of the speciv fied compound in the column entitled Coupling CIHB component, the dye resulting therefrom coloring In place of 7-methyl-N-glyceryl tetrahydrocellulose acetate the shades designated.

Table A i Coupling component iggifiggg t uli d 1 Barbituric i Greene 2 ammo 5m robenzenes Onaml e (2; 5,5-dimethyl-cyclohexandione-l,3- o? w (3) 1-pl1eny1-3-methyl-5-pyrazelone Orange-yellow. (4; B-methyI-fi-pyramlnm (5 Diphenylamine Violet-red.

6) Dimethylam' Do. (7) Methyl butyl aniline Do. (8) Methyl propyl aniline Do. (9) Eth l-m-toluidine Do. 0) B-H droxyethyl-anil1ne. Do. (11) D1-fl-hydroxyethyl-an1l1ne Do. 12) fl-Hy roxyethyl-m-toluidine Do. (13) fi-Sodium sulfoethyl propyl-m-toluidine ple. (14) Ethyl glyceryl-m-toluidine Violet'red. (15) B-Hydroxyethyl-In-anisidind. Do. (16) Ethyl glyceryl-m-anisidine Do. (17) Gresidinn D0, (18) Dibutyl cresidine Do thyl glyceryl cresld' Rubine (20) Glyceryl cresidine Do. (21) B-Sodium sulfatoethyl butyl cresidine. Violet-red. (22) fl-Hydroxyethyl glyceryl cresidine Plgple t0 violet- 116. (23) 5-Hydroxyethyl-mchloroaniline Wine. (24) fi-Sedium sulfate-butyl ethyl-m-chloroaniline Rubine. (25) Z-methoxy-5-chloro-fl-hydroxy-ethylaniline- Do. (26; 2-methoxy-6-chIoro-ethyl-glycerylaniline D0. (27 2-methoxy-fi-bromo-ethyl-B-sodium sulfoethylanilin Violet to purple. (28) 2,5-dlmethoxy-anilina Violet-red. (29) 2,5-d methoxy-B-sodium sulfoethyl butyl aniline Violet. (30) 2,5-dn'nethoxy-fl-sodium sulfatoethyl butyl aniline Purple. (31) 2,5-d1methyl-ethylaniline Violet-red. (32) Glyceryl-a-naphthylamine Violet. (33) N-glyceryl-7-methoxy-tetrahydroquinoline Do. (34) N fmethox y-fl-hydroxypropyl-7- methyl tetra hydro Do.

quino me. 2-amino-5-nitrobenzene sulfonmethylamide Couplers 1-34.. Same shad 2-a1nino-5-nitrobenzene sulfondimethylamidmn Couplers l34. D0 2-amino-5-nitrobenzene sulfondihydroxyethyl-am1de Couplers 1-34 Amine Coupling component gggggf fgg 2-amino-5-nitrobenzene sulfontetrahydrofurfurylamide Couplers 1-34 Do.

2-amino-5-nitrobenzeue sulfoncetylamide Couplers 1-34. Do.

Z-nmino-3-brorno-5-nitrobenzene sulfonmethylamida- Couplers 1-34 Do.

2-amino-3-chloto-5-nitrobenzeue sulfonmethylamide. Couplers 1-34. Do.

Z-amino-B, 5-dinitrobenzene-fl-hydroxyethylsulfonam di-fi-hydroxyethylomline. Rubine.

(36) B-Hydroxyethyl-m-toluidine Violet. (37; fl-Sodium sulioethyl propyl'm-toluidine... o. (38 fl-Hydroxyethyl-m-anisidine l. o. (39 Ethyl glyceryl cresidine Red-blue (40 Glyceryl cresidine Purple (41 fl-Sodium sulfatoethyl butyl cresid Red-blue (42) ,B-Hydroxyethyl glyceryl cresidine.-. Do. (43) B-Sodium sulfatobutyl ethyl-m-chloroaniline... Rubinc. 44) 2-methoxy-5-chloro-B-hydroxyethylaniline... Violet.

45) 2, S-dimethoxy-B-sodium sulfoethyl butyl aniline..- Do. 546) 2, fi-dimethoxy-B-sodium sulfatoethyl butylanilinc. Red-blue -17) Glyceryl-a-naphthylamine Blue. (48) N-glyceryl-Tmethoxy tetrshydroquinoline Do. (49) N y-methoxy-y-hydroxypropyl-7-methyl tetra-hydro- Do.

quinolinc.

2-amino-3,5-dinitrobenzene sulfonallylamide a. Couplers 35-49 2-arnino-3,5-diuitrobenzene sulfonethylamide. Couplers 3549.

2-amino-3,5-dinitrobenzene-suliondibutylamide Couplers 35-49" 2-amino-3,5-dinitrobenzenefi-sodmm sulloethyl sulfonamrde. Couplers 35-49 2-amino-3-methyl-5-nitro-benzene sulfonpropylamide Couplers 3549 Many of the dyes of our invention being watersoluble, they may be used for the direct coloration of organic derivatives of cellulose, particularly cellulose acetate in the form of threads, yarns, filaments and fabric materials, without the necessity of employing a dispersing or solubilizing agent. The dyeing operation will be conducted in accordance with the usual dyeing practice, salt being added if desired to facilitate exhaustion of the dye bath. For a more detailed description as to how the water-soluble azo dyes of our invention may be employed for the coloration of textile materials, reference may be had to our U. S. Patent No. 2,107,898, issued February 8, 1938.

In the case of the water-insoluble dyes of our invention, they are applied in the form of an aqueous suspension with ,a suitable dispersing agent such as soap. For example, the dye compound is finely grouped with a dispersing agent such as soap or oleyl glyceryl sulfate and the resulting paste is dispersed in water. The dispersion thus prepared is heated to a temperature approximately 45-55 C. and the cellulose acetate silk in the form of threads or fabric is immersed in the solution, after which the temperature is gradually raised to 80-85 C. and maintained at this point for several hours. Sodium chloride may be added as desired during the dyeing operation to promote exhaustion of the dyebath. Upon completion of the dyeing operation, the cellulose acetate silk is removed, washed with soap, rinsed and dried.

Typical organic derivatives of cellulose include,

the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters and cellulose mixed organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate, cellulose acetate-butyrate, and cellulose ethers such as methyl cellulose, ethyl cellulose, and benzyl cellulose.

The expression alkyl group as used throughout the specification and claims is intended to include the unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl and the like, as well as the substituted alkyl groups such as hydroxyethyl, dihydroxpropyl, methoxethyl, ethoxyethyl, acetoxyethyl, sulfoethyl, and sulfatoethyl groups.

The expression aryl group is intended to include the phenyl group, and substituted phenyl groups such as tolyl, xylyl, cresyl, nitrophenyl, chlorophenyl, and sulfophenyl groups.

The expression cycloalkyl group includes cyclohexyl and tetra hydronaphthalene groups; and heterocyclic group includes tetra hydrofurfuryl, quinoline groups, and the morpholine radical.

The expression acyl group is intended to include radicals containing a carbonyl group selected from the aliphatic and aromatic series such as the formyl group, the acetyl group, the propionyl group, the butyryl group, the benzoyl group, a naphthoyl group, the furoyl group, the palmityl group, and other similar type of radicals.

We claim:

1. The azo dye compounds having the general formula:

wherein Y represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, a nitro group, and the group R1, R2, R3 and R4 each represents a member selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an alkylene group, an aryl group of the benzene series, and a furyl group, X1 represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, and X2 represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, and the group -NHR5, wherein R5 represents a member selected from the group consisting of an acyl group, the group CON'H2, the group COCH2CN, the group -SO2CH3, and the group COOC2H5.

2. The azo dye compounds having the general formula:

R1 SO2N/ wherein R1, R2, R3 and R4 each represents a member selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an alkylene group, an aryl group of the benzene series, and a furyl group, X1 represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, and an alkoxy group, and X2 represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, and the group NHIR5, wherein R represents a member selected from the group consisting of an acyl group, the group C'ONH2, the group -COCH2CN, the group SO2CH3, and the group -COOC2H5.

3. The azo dye compounds having the general formula:

wherein R1, R2, R3 and R4 each represents a member selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an alkylene group, an aryl group of the benzene series and a furyl group, X1 represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, and an alkoxy group, and X2 represents a member selected from the group consisting of hydrogen, a halogen, an alkyl group, an alkoxy group, and the group NHR5, wherein R5 represents a member selected from the group consisting of an acyl group, the group CONH2, the group COCH2CN, the group -S02CH3, and the group --COOC2H5.

4. The azo dye compounds having the general formula:

N02 Xi consisting of an acyl group, the group -(|JNHa the group 1-oH1oN the group /-S GH$ 0 o and the group 5. The azo dye compounds having the general formula:

-oNH1 the group (I%CH1CN the group -SCH:

and the group ([%0C2Hs 6. The azo dye compounds having the general formula:

NO: OCH:

wherein R2, R3, and R4 each represents a member selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an alkylene group, an aryl group of the benzene series, and a furyl group,

'7. The azo dye compounds having the general formula:

S OaN wherein R2, R3, and R4 each represents a member selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an alkylene group, an aryl group of the benzene series, and a furyl group.

JAMES G. McNALLY. JOSEPH B, DICKEY. 

